EP4294874A1 - Utilisation d'un antioxydant pour réduire et/ou prévenir la toxicité d'une composition de caoutchouc - Google Patents
Utilisation d'un antioxydant pour réduire et/ou prévenir la toxicité d'une composition de caoutchoucInfo
- Publication number
- EP4294874A1 EP4294874A1 EP23722864.8A EP23722864A EP4294874A1 EP 4294874 A1 EP4294874 A1 EP 4294874A1 EP 23722864 A EP23722864 A EP 23722864A EP 4294874 A1 EP4294874 A1 EP 4294874A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tert
- diphenylamine
- group
- toxicity
- qsar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 230000002441 reversible effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
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- 231100000475 skin irritation Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
Definitions
- the present invention relates to the field of antioxidant additives used in rubber compositions, namely in elastomer compositions (macromolecular substance, natural or synthetic, having rubber elasticity).
- the present invention relates in particular to the use of specific polymeric antioxidants in a rubber composition in order to reduce and/or prevent its toxicity.
- rubber compositions generally comprise one or more additives including antioxidants.
- Anti-oxidants are also used in a large number of applications and common objects of daily life, and, despite their relatively modest content in the material in which they are incorporated, their contribution is essential. with regard to the lifespan and the conservation of the physicochemical and mechanical properties of these common objects.
- plastics, or even more specifically, rubbers used in pipes (parts under the hood for example), electrical cables or even tires their presence makes it possible to preserve the mechanical properties of the materials by notably avoiding their hardening by oxidation with air or ozone (case of tires subject to the action of ozone generated by heating of the air in contact with catalytic converters linked to road traffic).
- aromatic amines such as monomers of diphenylamines (DPA) or p-phenylenediamines (PPD) are very widely used in rubber pipes, cables or tires.
- DPA diphenylamines
- PPD p-phenylenediamines
- This last family (PPD) today constitutes a range of additives of choice for its antioxidant and antiozonant properties necessary for tires subject to these two aging phenomena.
- the compound N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine (hereinafter 77PD, CAS 3081-14-9) is commonly used for rubber coatings on electrical cables.
- Document FR 2 156 392 describes antioxidant products for materials such as rubber (page 6, line 1-4) such as 2-(4,4'-di-t-octyldiphenylamino)-4 ,4'-di-t-octyldiphenylamine.
- This document only cites rubbers in general terms, in the same way as plastics, without ever supporting their description, as well as the effectiveness of anti-oxidants. in such compositions which are, unlike lubricating compositions, in the solid state. Only performance in the field of fluids and lubricants is demonstrated.
- Document CN 107 540 559 describes a process for preparing 4,4'-bis(a,a-dimethylbenzyl)diphenylamine.
- Document EP 2 842 995 relates to a specific material for the manufacture of a special run-flat tire rubber for a wheeled military combat vehicle. To the Applicant's knowledge, the rubber industry only uses monomeric compounds (substances) as antioxidants and not polymers/oligomers.
- Document WO 2009/071857 relates to a process for preparing an antioxidant and/or anti-corrosion agent for lubricating oil comprising diphenylamine and phenyl-a-naphthylamine units.
- the Applicant has endeavored to develop compounds having both antioxidant properties, while making it possible to prevent and/or reduce the toxicity of a rubber composition in which they are incorporated, at the same time with regard to that of standard antioxidants, such as those mentioned above belonging in particular to the family of diphenylamine (DPA) or p-phenylenediamine (PPD) monomers.
- DPA diphenylamine
- PPD p-phenylenediamine
- document CN 107 540 559 describes that the compound 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, which is a monomer of diphenylamines (DPA) would be non-toxic.
- DPA diphenylamine
- PPD p-phenylenediamine
- the Applicant has notably demonstrated, in a surprising and unexpected manner, that once oligomerized and/or polymerized, the toxicity of diphenylamine monomers is drastically reduced. They thus make it possible to form oligomers and/or polymers comprising at least one diphenylamine repeat unit having both antioxidant and even antiozonant properties, adapted to the various areas of use of rubber composition (tires, electric cables, etc.), while being slightly or not at all toxic to humans and/or the environment.
- oligomers/polymers that is to say macromolecules
- an antioxidant effect similar to monomers or substances which are by definition more mobile and more active in theory in solid rubber compositions. It is important to distinguish a solid, crosslinked material from a fluid through which it is easier for a soluble antioxidant to act.
- the high performance technical reference as an antioxidant in rubber (tire) compositions is the compound described in document CN 107 540 559, namely 4,4'-bis (a,a-dimethylbenzyl)diphenylamine (CAS 10081-67-1 corresponding to the product Naugard® 445).
- this compound is toxic, unlike the compounds of the invention.
- Other substances commonly used in this field are 6PPD (comparative compound 22) and IPPD (comparative compound 23). These two compounds are also toxic, one is even a CMR compound according to the European regulations in force. Thus, the particular technical effect of the compounds according to the invention could not be predicted from the teachings of the prior arts.
- the present invention relates to the use of at least one antioxidant in a rubber composition, said at least antioxidant comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I ): wherein each of R1 to R10 is independently selected from a hydrogen atom, an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms and an aralkyl group which is an alkyl group as described above of which at least one of the carbon atoms is substituted by a monocyclic or polycyclic aromatic hydrocarbon aryl group comprising 5 to 14 carbon atoms, to reduce and/or prevent the toxicity of said rubber composition.
- each of R1 to R10 is independently selected from a hydrogen atom, an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms and an aralkyl group which is an alkyl group as described above of which at least one of the carbon atom
- the term “comprising” and its derivatives must be understood as non-limiting and not excluding the presence of other components or steps.
- the term “understand” can be understood as “being essentially made up of” or “being made up of”.
- the present invention thus relates to the use of at least one antioxidant in a rubber composition, said at least antioxidant comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I ): in which each of R1 to R10 is independently chosen from: a hydrogen atom, an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms and an aralkyl group which is an alkyl group such as described above, at least one of the carbon atoms of which is substituted by a monocyclic or polycyclic aromatic hydrocarbon aryl group comprising 5 to 14 carbon atoms, to reduce and/or prevent the toxicity of said rubber-based composition.
- each of R1 to R10 is independently chosen from: a hydrogen atom, an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms and an aralkyl group which is an alkyl group such as described above, at
- antioxidant we mean specialty chemical additives which serve to interrupt the degradation process linked to oxidation in compositions in which they are integrated, in the present case rubber compositions.
- toxicity of a substance and/or a composition
- said substance and/or said composition presents at least one, preferably at least two, in particular at least three and typically at least four, such as at least five, at least six, or even all of the following toxicities:
- - neurotoxicity which is the ability of a substance or compound to induce harmful effects in the nervous system of a mammal/living being, such as humans or planarians,
- a compound having a CMR character thus presents various toxicities.
- the toxicity thus comprises one or more of the following toxicities: neurotoxicity, reprotoxicity, mutagenicity, acute toxicity, carcinogenicity, toxicity on synthesis, degradation, transport and the mode of action of hormones and ecotoxicity.
- “Reducing” the toxicity of a rubber composition means that said at least one antioxidant according to the invention (namely comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I)) is capable and/or configured to reduce the toxicity of a rubber composition in which it is included, namely by its presence, in particular compared to other possible generally toxic standard antioxidant compounds, that said at least one oxidant according to the invention comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I) makes it possible to lower/reduce the toxicity of a rubber composition and to obtain a non-toxic or at least reduced toxicity rubber composition.
- “Preventing” the toxicity of a rubber composition means said at least antioxidant according to the invention comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I) allows to prevent the rubber composition from being considered toxic and/or to prevent the appearance of toxic symptoms in a mammal or any other living being, such as a human being or an animal, which would be in contact with said rubber composition.
- neurotoxic symptoms can, for example, affect the central nervous system (CNS) and present the following effects: headaches, loss of appetite, drowsiness, mood and personality disorders.
- cognitivos learning and concentration disorders
- PNS peripheral nervous system
- motor impairment such as weakness, tremors, incoordination, convulsions, etc.
- sensory impairment such as decreased hearing, color vision, tinnitus, loss of balance, etc.
- symptoms of acute toxicity may be skin irritation, allergic skin reaction, vomiting, etc.
- said at least one antioxidant according to the invention namely comprising at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I)
- said at least one antioxidant according to the invention is capable of and/or configured to reduce and/or prevent the toxicity of a rubber composition at the different stages of the life of said rubber composition, namely its implementation, its use and its end of life including spreading in the environment (such as particles , or the wear of a tire made from said composition).
- said oligomer and/or polymer comprising at least one diphenylamine repeat unit of general formula (I) may also comprise at least one phenyl a-naphthylamine repeat unit of general formula (II): wherein each of R11 to R22 is independently selected from: a hydrogen atom and an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms.
- polymer of at least one diphenylamine and optionally at least one phenyl a-naphthylamine, we designate in the present invention a compound comprising the repetition of at least two diphenylamine units with optionally at least one phenyl a- unit. naphthylamine.
- oligomer of at least one diphenylamine and optionally at least one phenyl a-naphthylamine
- a polymer of at least one diphenylamine and optionally at least one phenyl a-naphthylamine which comprises between 2 and 15 repeat units, or a mixture of such compounds. It may in particular be a dimer, a trimer, a tetramer, a pentamer, a hexamer, a heptamer, an octamer, a nonamer, a decamer and/or any mixture of such compounds.
- the oligomer contains (in relative %) at least 70%, preferably 80% and in particular 90% by mass of dimer, trimer, tetramer, pentamer or a mixture of such compounds.
- the oligomer corresponds to a dimer and/or a trimer.
- diphenylamine or phenyl a-naphthylamine we designate the fact that, in the final structure of the oligomer or polymer obtained according to the invention, at least one diphenylamine unit and at least one are present. phenyl a-naphthylamine unit, or at least two diphenylamine units with optionally at least one phenyl a-naphthylamine unit.
- the diphenylamine and phenyl a-naphthylamine repeat units can be positioned in any case relative to each other in the structure of the polymer or oligomer according to the invention.
- the polymer or oligomer may comprise, at least on part of its structure, a regular alternation of diphenylamine and phenyl a-naphthylamine repeat units. It may comprise, at least on part of its structure, a random distribution of the diphenylamine and phenyl a-naphthylamine repeat units. It can finally comprise, on at least part of its structure, a block comprising a single type of diphenylamine or phenyl a-naphthylamine repeat unit.
- the polymer and/or oligomer according to the invention only comprises diphenylamine and phenyl a-naphthylamine repeat units in its structure. In another embodiment, the polymer and/or oligomer according to the invention only comprises diphenylamine repeat units in its structure.
- each of R1 to R10 is independently chosen from: a hydrogen atom, an alkyl group (which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms) and an aralkyl group (which is a group alkyl as described above in which at least one of the carbon atoms is substituted by a monocyclic aryl or polycyclic aromatic hydrocarbon group comprising 5 to 14 carbon atoms).
- the at least one diphenylamine of formula (I) is an alkylated diphenylamine, that is to say that at least one of R1 to R10 is an alkyl or aralkyl group.
- at least one of R1 to R5 is an alkyl or aralkyl group
- at least one of R6 to R10 is an alkyl or aralkyl group.
- each of R1 to R10 is independently chosen from: a hydrogen atom or an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms, preferably comprising from 1 to 15 carbon atoms, in particular from 3 to 12 carbon atoms and typically from 3 to 10 carbon atoms.
- said at least three substituents can be, independently of each other, a tert-butyl group or a tert-octyl group or even an n-nonyl group.
- At least one, in particular at least two and typically at least three, substituents among R1 to R10 is an alkyl group (as defined below), the other substituents being a hydrogen atom.
- less than nine, especially less than six and typically less than four of the substituents among R1 to R10 is an alkyl group, the other substituents being a hydrogen atom.
- “at least one” includes the following numbers and all intervals between these values: 1; 2; 3; 4; 5; 6; 7; 8; 9; 10.
- “less than nine” includes the following numbers and all intervals between these values: 9; 8; 7; 6; 5; 4;3; 2; 1.
- one or two substituents among R1 to R10 is an alkyl group, the other substituents being a hydrogen atom.
- alkyl is meant in the present invention a saturated hydrocarbon group, linear, branched or cyclic, comprising from 1 to 24 carbon atoms.
- an alkyl group comprises from 1 to 12 carbon atoms.
- an alkyl comprising 1 to 24 carbon atoms includes the following carbon numbers and all the intervals between these values: 1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 1 5; 16; 17; 18; 19; 20; 21; 22; 23; 24.
- alkyl groups mention may in particular be made of the methyl group, the group ethyl, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, iso-butyl group, n-pentyl group, iso-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, tert-octyl group, iso-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n- group dodecyl and the isododecyl group.
- an alkyl group is chosen from the group consisting of the tert-butyl group and the tert-octyl group, or even the n-nonyl group (nC9), and can be chosen from the group consisting of the tert-butyl group and tert-octyl group.
- aralkyl is meant in the present invention an alkyl group in which at least one of the carbon atoms is substituted by an aryl group.
- aryl group is meant in the present invention a monocyclic or polycyclic aromatic hydrocarbon group.
- Each aromatic or polyaromatic ring includes 5 to 14 atoms.
- Examples of aryl groups include the phenyl group.
- the diphenylamine of formula (I) is chosen from the group consisting of N,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine, N,N -di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine, N-(p-tert- butylphenyl)-N-(p-tert-octylphenyl)amine, tert-butylated and/or tert-octyl diphenylamines, nonylated diphenylamines, and any mixture thereof.
- the polymer or oligomer according to the present invention only comprises diphenylamine units.
- the oligomer comprising at least one diphenylamine repeat unit of general formula (I) according to the invention can thus be a dimer, a trimer, a tetramer, a pentamer of one or more of these diphenylamines of formula (I) described above and correspond by way of example to a dimer or trimer of di-(p-tert-octylphenyl)amine (DODPA).
- DODPA di-(p-tert-octylphenyl)amine
- the oligomer comprising at least one diphenylamine repeat unit of general formula (I) according to the invention when it is a dimer, it has at least three, generally at least four, substituents among all the substituents R1 to R10 of the repeating unit of formula (I) forming the dimer which are not a hydrogen atom (the other substituents are thus hydrogen atoms).
- “at least three substituents among R1 to R10 of the repeating unit of formula (I) forming the dimer” comprises the following values: 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20 and can correspond for example to three or four substituents among all the substituents R1 to R10 forming the dimer.
- said at least three substituents are preferably each an alkyl group, ie: saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms, preferably comprising from 3 to 15 carbon atoms, in particular from 5 to 12 carbon atoms and typically 6 to 9 carbon atoms.
- said at least three substituents can be, independently of each other, a tert-butyl group or a tert-octyl group or even an n-nonyl group.
- said at least three Substituents are independently distributed over the two diphenylamine repeat units of formula (I) of the dimer.
- each repeat unit comprises at least one of said three substituents.
- a repeating unit of the dimer comprises at least one substituent from R1 to R10 which is not a hydrogen atom (and is preferably an alkyl group as defined above) and the other unit of the dimer comprises at least two substituents among R1 to R10 which is not a hydrogen atom (and is preferably an alkyl group as defined above).
- the oligomer comprising at least one diphenylamine repeat unit of general formula (I) according to the invention when it is a trimer, it has at least one, preferably at least two, substituents among all the substituents.
- R1 to R10 of the repeating unit of formula (I) forming the trimer which is not a hydrogen atom (the other substituents are thus hydrogen atoms).
- “at least one substituent among all the substituents R1 to R10 of the repeating unit of formula (I) forming the trimer” comprises the following values: 1, 2, 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13; 14; 15; 16; 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27; 28; 29; 30 and can correspond for example to five or six substituents among all the substituents R1 to R10 forming the trimer.
- said at least one, preferably five, or even six substituents are generally each an alkyl group, i.e.: saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms, preferably comprising from 3 to 15 carbon atoms , in particular from 5 to 12 carbon atoms and typically from 6 to 9 carbon atoms.
- said substituent(s) may be, independently of each other, a tert-butyl group or a tert-octyl group or even an n-nonyl group and is typically a tert-octyl group.
- each repeating unit of the trimer comprises at least one, or even two, substituents from R1 to R10 which is an alkyl group as defined above (the other substituents being hydrogen atoms).
- said alkyl substituent(s) are independently distributed over the three diphenylamine repeat units of formula (I) of the trimer.
- each repeating unit of the trimer comprises at least one, or even two, alkyl substituents (the other substituents being hydrogen atoms).
- the diphenylamines according to the invention can be presented isolated, or mixed together.
- they can be in the form of a mixture of N,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine, N,N-di-(p-tert-octylphenyl) )amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine and N-(p-tert-butylphenyl)-N-(p-tert -octylphenyl)amine, tert-butylated and/or tert-octyl diphenylamines, nonylated diphenylamines.
- oligomers and/or polymers comprising at least one diphenylamine repeat unit of general formula (I) may correspond to the compounds exemplified below.
- Phenyl a-naphthylamine denotes according to the present invention a compound of formula (II): wherein each of R11 to R22 is independently selected from: a hydrogen atom and an alkyl group which is a saturated, linear or branched hydrocarbon group comprising from 1 to 24 carbon atoms.
- At least one of R11 to R22 is an alkyl group. In one embodiment, only one of R11 to R22 is an alkyl group, in particular a tert-octyl group.
- the phenyl a-naphthylamine is N-(4-tert-octylphenyl)-1-naphthylamine, with CAS number 4572-51-4 (OPAN).
- the at least one diphenylamine is in the form of a mixture of N,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine, N,N- di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine and N-( p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine, and the at least one phenyl a-naphthylamine is N-(4-tert-octylphenyl)-1-naphthylamine (OPAN).
- the at least one diphenylamine is di-(p-tert-octylphenyl)amine (DODPA) and the at least one phenyl a-naphthylamine is N-(4- tert-octylphenyl)-1-naphthylamine (OPAN).
- DODPA di-(p-tert-octylphenyl)amine
- OPAN N-(4- tert-octylphenyl)-1-naphthylamine
- the oligomer forming the antioxidant according to the invention can thus correspond to a 2DODPA/1OPAN, 1DODPA/2OPAN, 3DODPA trimer.
- said at least oligomer may correspond to a mixture of trimers, such as a mixture of 2DODPA/1OPAN, 1DODPA/2OPAN and 3DODPA.
- the 2DODPA/1OPAN oligomer is in the majority.
- said at least oligomer comprises a mixture of trimers (such as 2DODPA/1OPAN, 1DODPA/2OPAN, 3DODPA), tetramers, pentamers and hexamers.
- the relative proportions by mass of the two types of diphenylamine and phenyl a-naphthylamine units within the polymer or the oligomer can vary to a large extent from 0/100 to 100/0.
- the relative proportion by mass of diphenylamine/phenyl a-naphthylamine is between 100/0 and 10/90, in particular between 100/0 and 30/70 (such as 50/50 or 80/20), in particular between 100/0 and 90/10 and typically between 100/0 and 95/5.
- the polymer or oligomer according to the present invention forming said at least antioxidant according to the invention can in particular be prepared according to the process described in the application patent FR 2010199 filed by the Applicant company, namely in a continuous reactor. Those skilled in the art are able to adjust the quantities of diphenylamine and phenyl a-naphthylamine to be introduced into the reactor depending in particular on the desired structure of the oligomer or polymer to be synthesized and the desired thermal characteristics.
- the polymer or oligomer according to the present invention forming said at least antioxidant according to the invention can in particular also be prepared according to the process described in document US 2019/0127526 or even document WO 2008/022028.
- the Applicant has demonstrated the non-toxicity of said at least one antioxidant comprising at least one oligomer and/or a polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat motif of formula (II) according to the invention by QSAR modeling tests for neurotoxicity, for reprotoxicity, for mutagenicity and carcinogenicity.
- the oligomer and/or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) has a QSAR value for the measurement of each of the following toxicities: neurotoxicity (neurotoxic QSAR), reprotoxicity (reprotoxic QSAR), mutagenicity (mutagenic QSAR) and carcinogenicity (carcinogenic QSAR), corresponding to a statistical threshold value (%) subtracted from a delta of at least 30%, said statistical threshold value being determined, for each of said toxicity, by QSAR (quantitative structure-activity relationship) modeling (from the English “Quantitative Structure Activity Relationship”) according to the method described below in the experimental part,
- a delta of at least 30% for QSAR modeling includes the following values and all the intervals between these values: 30; 31; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51; 52; 55; 60; 65; 70; 75; 80; 85; 90; 91; 92; 93; 94; 95; 96; 97; 98; 99; 100 (this range of at least 30% must be adapted for each toxicity).
- the statistical threshold value of the neurotoxic QSAR as a percentage is typically 55%.
- the delta for measuring the neurotoxic QSAR is at least 45%, advantageously at least 55% and typically at least 53%.
- the oligomer and/or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) has a percentage value (% ) by modeling QSAR less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 2% for the measurement of neurotoxicity (neurotoxic QSAR).
- a value less than or equal to 10% for neurotoxic QSAR modeling includes the following values and all the intervals between these values: 10; 9; 8; 7; 6; 5; 4; 3; 2; 1; 0.9; 0.8; 0.70; 0.69; 0.68; 0.67; 0.66; 0.65; 0.64; 0.63; 0.62; 0.61; 0.60; 0.59; 0.58; 0.57; 0.56; 0.55; 0.54; 0.53; 0.52; 0.51; 0.50; 0.49; 0.48; 0.47; 0.46; 0.45; 0.44; 0.42; 0.40; 0.38; 0.36; 0.34; 0.32; 0.30; 0.28; 0.26; 0.24; 0.22; 0.20; 0.18; 0.16; 0.14; 0.12; 0.10; 0.09; 0.08; 0.07; 0.06; 0.005; 0.04; 0.03; 0.02;0.01; 0.00.
- the QSAR reprotoxic statistical threshold value as a percentage is typically 90%.
- the delta for measuring the reprotoxic QSAR is at least 41%, advantageously at least 43% and typically at least 46%.
- the oligomer and/or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) has a percentage value ( %) by modeling QSAR less than or equal to 65%, preferably less than or equal to 50% and typically less than or equal to 45% for the measurement of reprotoxicity (reprotoxic QSAR).
- a value less than or equal to 65% for reprotoxic QSAR modeling includes the following values and all the intervals between these values: 65; 64; 63; 62; 61; 60; 59; 58; 57; 56; 55; 54; 53; 52; 51; 50; 49; 48; 47; 46; 45; 44; 43; 42; 41; 40; 39; 38; 37; 36; 35; 34; 33; 32; 31; 30 ; 29; 28; 27; 26; 25; 24; 23; 22; 21; 20; 15; 10; 5; 3; 1; 0.50; ; 0.49; 0.48; 0.47; 0.46; 0.45; 0.44; 0.42; 0.40; 0.38; 0.36; 0.34; 0.32; 0.30; 0.28; 0.26; 0.24; 0.22; 0.20; 0.18; 0.16; 0.14; 0.12; 0.10; 0.09; 0.08; 0.07; 0.06; 0.005; 0.04; 0.03; 0.02;0.01; 0.00.
- the statistical threshold value (mutagenic QSAR as a percentage is typically 58%.
- the delta for measuring the mutagenic QSAR is at least 48%, advantageously at least 53% and typically at least 56%.
- the oligomer and/or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) has a percentage value (% ) by modeling QSAR less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 2% for the measurement of mutagenicity (mutagenic QSAR).
- a value less than or equal to 10% for mutagenic QSAR modeling includes the following values and all the intervals between these values: 10; 9; 8; 7; 6; 5; 4; 3; 2; 1; 0.9; 0.8; 0.70; 0.69; 0.68; 0.67; 0.66; 0.65; 0.64; 0.63; 0.62; 0.61; 0.60;
- the carcinogenic QSAR statistical threshold value as a percentage is typically 85%.
- the delta for measuring the carcinogenic QSAR is at least 77%, advantageously at least 82% and typically at least 85%.
- the oligomer and/or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) has a percentage value ( %) by QSAR modeling less than or equal to 10%, preferably less than or equal to 5% and typically less than or equal to 2% for the measurement of carcinogenicity (carcinogenic QSAR).
- a value less than or equal to 10% for carcinogenic QSAR modeling includes the following values and all the intervals between these values: 10; 9; 8; 7; 6; 5; 4; 3; 2; 1; 0.9; 0.8; 0.70; 0.69; 0.68; 0.67; 0.66; 0.65; 0.64; 0.63; 0.62; 0.61; 0.60;
- rubber composition we generally designate an elastomeric composition comprising, by definition, macromolecular substances, natural or synthetic, having rubber elasticity.
- elastomer is meant a polymer having elastic properties, obtained after crosslinking.
- Rubber/elastomer means an elastic, impermeable and resistant substance obtained by coagulation of the latex of certain plants, trees or lianas from the equatorial forest, or prepared synthetically, by polymerization of various unsaturated hydrocarbons.
- the current classification consists of separating rubbers into three main categories (the acronyms used are those recommended by standard ISO 1629 of 1995):
- NR natural rubber
- IR synthetic polyisoprene
- SBR styrene butadiene copolymers
- BR polybutadienes
- CM chlorinated and chlorosulfonated polyethylenes
- CM chlorinated and chlorosulfonated polyethylenes
- ACM polyacrylates
- EVM ethylene vinyl acetate copolymers
- AEM ethylene methyl acrylate
- HNBR hydrogenated nitrile rubbers
- CO epichlorohydrin rubbers
- CO ECO, GECO
- AU EU
- thermoplastic elastomers which form a separate category. In fact, compared to the rubbers previously mentioned, these elastomers do not need to be vulcanized and are used like thermoplastics.
- natural rubber comes from the coagulation of the latex of several plants, mainly the rubber tree, Hevea brasiliensis, family Euphorbiaceae, native to Amazonia. Collection is done by incising the bark of the trunks so that the latex, coming from the laticiferous canals, flows into buckets placed just below. The harvested latex is transferred into containers, filtered and can then be stabilized with ammonia (precipitation of the flakes) then pressed to reduce its water content or coagulated in a more or less controlled manner and dried by the smoke of a fire. (the tars prevent putrefaction) in order to obtain rubber balls.
- ammonia precipitation of the flakes
- synthetic rubber can be manufactured from the polymerization of various monomers, including isoprene (2-methyl-1,3-butadiene), 1,3-butadiene, chloroprene (2-chloro-1,3-butadiene), and isobutylene (methylpropene) with a small percentage of isoprene for crosslinking.
- monomers including isoprene (2-methyl-1,3-butadiene), 1,3-butadiene, chloroprene (2-chloro-1,3-butadiene), and isobutylene (methylpropene) with a small percentage of isoprene for crosslinking.
- monomers can be mixed in various desirable proportions to be copolymerized for a wide range of physical, mechanical and chemical properties.
- Monomers can be produced pure, and the addition of impurities or additives can be controlled by design to provide optimal properties.
- the polymerization of pure monomers can be better controlled to give a desired ratio of cis and trans double bonds
- a rubber composition or an elastomeric composition means a composition comprising mainly rubber, namely a composition comprising, by mass, at least 60%, preferably at least 70%, in particular at least 80% and typically at least 90% rubber.
- said rubber composition and/or said at least antioxidant additive does not substantially comprise, preferably does not comprise, diphenylamine monomers (DPA) or p-phenylenediamines (PPD) or any other standard antioxidant. (toxic and/or ecotoxic) mentioned above in the description of the prior art, whatever it may be.
- the rubber composition used according to the invention or the anti-oxidant agent used according to the invention does not substantially comprise, preferably does not comprise, any anti-oxidant additive other than the oligomer and /or the polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) according to the invention.
- the anti-oxidant additive according to the invention represents, by mass, relative to the total mass of the anti-oxidant agents present in the rubber-based composition, from 50% to 100%, preferably from 80% to 100%, and in particular from 90% to 100% and typically 100%.
- 50% to 100% we mean the following values or any interval between these values: 50; 55; 60; 65; 70; 75; 80; 85; 90; 95; 100.
- Said at least one anti-oxidant agent and generally said at least one oligomer and/or polymer comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) is present in the rubber-based composition used in the present invention in an amount such as those conventionally used in the art. For example, they can be used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, typically 1 to 4% relative to the total weight of said rubber composition.
- the rubber composition may also include other additives, such as mineral solid fillers for reinforcing the mechanical properties, carbon black, plasticizers, vulcanization agents (such as elemental sulfur or polythiols), vulcanization accelerators, crosslinking retarders, silanes and other agents capable of increasing the degree of crosslinking, etc.
- additives such as mineral solid fillers for reinforcing the mechanical properties, carbon black, plasticizers, vulcanization agents (such as elemental sulfur or polythiols), vulcanization accelerators, crosslinking retarders, silanes and other agents capable of increasing the degree of crosslinking, etc.
- additives will not be described in more detail below because their composition and conditions of use (mass content, etc.) are known to those skilled in the art depending on the intended uses of the rubber-based composition.
- the present invention can also be applied to a process for preserving the physicochemical and mechanical properties of a rubber-based composition comprising:
- said rubber composition which preferably does not comprise diphenylamine monomers (DPA) or p-phenylenediamines (PPD),
- At least one antioxidant comprising an oligomer and/or polymer comprising at least one diphenylamine repeat unit of formula (I) as defined above and optionally at least one unit repeating phenyl a-naphthylamine of formula (II) as defined above, said at least antioxidant being capable of reducing and/or preventing the toxicity of said rubber-based composition.
- the term “approximately” a value V designates an interval between 0.9xV and 1.1xV. In certain embodiments, it designates an interval between 0.95xV and 1.05xV, in particular an interval between 0.99xV and 1.01xV.
- oligomers and/or polymers comprising at least one diphenylamine repeat unit of formula (I) and optionally at least one phenyl a-naphthylamine repeat unit of formula (II) according to the invention have been studied and compared to d other standard antioxidant compounds, in terms of QSAR modeling for neurotoxicity, reprotoxicity, mutagenicity and carcinogenicity.
- test molecules were defined with chemical structures compiled from several publicly available sources such as: HSBD (Hazardous Substances Data Bank), EPA (US Environmental Protection Agency), ECHA (European Chemicals Agency) and NTP (National Toxicology Program). Around 34,000 molecules were selected for this project including: 3245 compounds classified as neurotoxic compounds, 12609 compounds classified as reprotoxic compounds, 4084 compounds classified as mutagenic compounds, 12158 compounds classified as carcinogenic compounds and 1953 compounds, called non-toxic, classified as neither neurotoxic, nor reprotoxic, nor mutagenic, nor carcinogens.
- HSBD Hazardous Substances Data Bank
- EPA US Environmental Protection Agency
- ECHA European Chemicals Agency
- NTP National Toxicology Program
- test molecules From this set of test molecules, two sets of molecules were defined: a training set and a validation set. To do this, the “leave one out” method was used. The set of test molecules was divided into two sets, one containing 90% of the test molecules and forming the training set; and the other, containing the 10% of the remaining test molecules, and forming the validation set.
- a generalized linear model (GLM) method was chosen to carry out a quantitative structure/activity relationship (QSAR) approach.
- the GLM models were trained separately to discriminate the chemical structures (i) between neurotoxic and non-neurotoxic compounds, (ii) between reprotoxic and non-reprotoxic compounds, (iii) between mutagenic and non-mutagenic compounds.
- -mutagenic and (iv) between carcinogenic and non-carcinogenic compounds This approach resulted in four GLM models with 328, 313, 327 and 330 significant descriptors within the neurotoxic, reprotoxic, mutagenic and carcinogenic training sets, respectively.
- ROC Receiver Operator Characteristic
- the neurotoxicity categories of the compounds in the validation set i.e. the neurotoxic/non-neurotoxic categorization
- the categories of reprotoxicity of the compounds in the validation set i.e. the reprotoxic/non-reprotoxic categorization
- the categories of mutagenicity of the compounds in the validation set i.e. the mutagenic categorization and non-mutagenic
- the categories of carcinogenicity of the compounds in the validation set i.e. carcinogenic and non-carcinogenic categorization.
- the performance of the QSAR models was measured by area under the curve (AUC) values and provided significant values of 0.76 and above for the prediction of neurotoxicity, mutagenicity and carcinogenicity. and provided significant values of 0.70 and above for the prediction of reprotoxicity.
- AUC area under the curve
- This statistical threshold is a first outline making it possible to distinguish non-toxic, moderately toxic molecules and toxic molecules. However, it does not allow toxic molecules to be completely excluded from non-toxic molecules, i.e. the margin of error on the probability of the risk of toxicity).
- the Applicant thus refined its research and determined that a reduction in the statistical threshold by a delta of 30% for each model (neurotoxic QSAR, reprotoxic QSAR, etc.) made it possible to reliably guarantee the toxicity or not of the molecules tested. Indeed, this new threshold (statistical threshold -30%) makes it possible to indisputably exclude moderately toxic and residual toxic molecules from non-toxic molecules. Also, an intermediate fringe (non-zero probability of toxicity) including moderately toxic and/or toxic residual molecules was established in order to establish a more precise classification.
- the examples named A to I are according to the invention and the examples named 1 to 26 are comparative examples (standard anti-oxidants and anti-ozonants).
- the anti-oxidants comprising an oligomer and/or polymer comprising at least one diphenylamine repeat unit and optionally at least one phenyl a-naphthylamine repeat unit according to the invention present at least one both very low neurotoxicity, reprotoxicity, mutagenicity and low carcinogenicity.
- the compounds making up standard anti-ozonant antioxidants are generally highly toxic, whether in terms of neurotoxicity, reprotoxicity, mutagenicity and/or carcinogenicity.
- This QSAR modeling test therefore demonstrates that the oligomers and/or polymers comprising at least one diphenylamine repeat unit and optionally at least one phenyl a-naphthylamine repeat unit according to the invention make it possible to prevent and/or reduce toxicity. of a rubber-based composition.
- Control points lethality, adhesion (production of sticky mucus by the skin leading the planarian to be stuck to a wall rather than floating), speed of movement, rest (pro rata of rest time compared to time spent traveling), phototaxis and “scrunching” (specific mode of movement nominally used by the planarian in the event of danger, here excessive heat).
- adhesion production of sticky mucus by the skin leading the planarian to be stuck to a wall rather than floating
- speed of movement rest (proportion of rest time compared to time spent moving)
- phototaxis and “scrunching” (specific mode of movement nominally used by the planarian in the event of danger, here excessive heat).
- HNBR rubber which is a hydrogenated butadiene-acrylonitrile rubber
- AEM rubber VAMAC® which is an ethylene acrylic rubber
- HNBR type rubbers are formulated according to the composition summarized in Table 7 below (the proportions are indicated in pce: percentage of elastomer): Table 7]
- AEM type rubbers are formulated according to the composition summarized in Table 8 below (the proportions are indicated in pce: percentage of elastomer): Table 8]
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Abstract
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FR2203941A FR3135084A1 (fr) | 2022-04-27 | 2022-04-27 | Utilisation d’un antioxydant pour réduire et/ou prévenir la toxicité d’une composition de caoutchouc |
PCT/EP2023/061024 WO2023209042A1 (fr) | 2022-04-27 | 2023-04-26 | Utilisation d'un antioxydant pour réduire et/ou prévenir la toxicité d'une composition de caoutchouc |
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US3592622A (en) | 1968-06-05 | 1971-07-13 | Air Reduction | Oxy-fuel accelerated glass melting furnace and method of operation |
GB1377195A (en) * | 1971-10-16 | 1974-12-11 | Ciba Geigy Ag | Anti-oxidant composition |
US7413682B2 (en) | 2006-08-15 | 2008-08-19 | Anderol, Inc. | Antioxidants and methods of making antioxidants |
FR2924122B1 (fr) * | 2007-11-28 | 2009-12-25 | Nyco Sa | Agent anti-oxydant et/ou anti-corrosion, composition lubrifiante contenant ledit agent et procede pour preparer celui-ci |
CN102627791A (zh) * | 2012-04-16 | 2012-08-08 | 夏华松 | 用于制造军队轮式战车、飞机特种安全轮胎橡胶的专用材料 |
CN107540559A (zh) * | 2017-08-29 | 2018-01-05 | 蔚林新材料科技股份有限公司 | 一种抗氧剂4,4’‑双(α ,α‑二甲基苄基)二苯胺的制备方法 |
US20190127526A1 (en) | 2017-10-31 | 2019-05-02 | Basf Se | Antioxidant Polymeric Diphenylamine Compositions |
US20200209223A1 (en) | 2019-01-02 | 2020-07-02 | Eva-Maria S. Collins | High throughput method and system for analyzing the effects of agents on planaria |
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